Thermodynamic study of inclusion complexes of zaleplon with natural and modified cyclodextrins

The thermodynamics and stoichiometry of zaleplon (ZAL) complexation with different cyclodextrin derivatives [β-CD, hydroxypropyl-β-cyclodextrin (HP-β-CD), randomly methylated-β-cyclodextrin (RAMEB), sulphobutylether-β-cyclodextrin (SBE-β-CD)] in aqueous solution was studied by spectrofluorimetry and ¹H NMR spectroscopy in order to obtain a more general understanding of the driving forces behind the inclusion phenomena. Job’s plot derived from the NMR spectral data and statistical analysis of spectrofluorimetric titration data confirmed the formation of equimolar complexes in all systems tested, excluding the possibility of higher order complex formation. Furthermore, thermodynamic parameters obtained by both techniques gave similar and negative values of ΔG° for all complexes, indicating spontaneous inclusion of drug into CDs. From a thermodynamic point of view, two types of inclusions were determined. One is enthalpy driven ZAL complexation with β-CD, HP-β-CD and RAMEB, while the other is entropy driven complexation observed in the case of SBE-β-CD. The mechanisms behind each type of inclusion were discussed in detail.     

Evaluation of a method for treatment of iron gall ink corrosion on paper

Iron gall ink was the most widely used writing ink for paper from the Middle Ages to the twentieth century. Unfortunately, the ink ingredients contain corrosive transition metal ions and acids that cause severe damage to the paper carrier. New or improved paper conservation methods for iron gall ink stabilization are constantly sought. The aim of the study was evaluation of a recently proposed stabilization treatment, adapted to lower relative humidity, applied to various model and historical paper samples containing iron gall ink. The effect of stabilization treatment on paper samples during artificial thermal aging was followed by the determination of the molecular weight distribution by size exclusion chromatography and colorimetry. Migration of iron and copper compounds from the ink lines was monitored by laser ablation inductively coupled plasma mass spectrometry. The results demonstrate that effective stabilization of iron gall ink-containing paper can be successfully achieved by interleaving with papers impregnated with the antioxidant tetrabutylammonium bromide and alkaline buffer under experimental conditions. Negative side effects of the stabilization treatment, such as migration of iron or copper ions from the ink lines and changes of color after the treatment and after accelerated thermal degradation, were limited, proving that the proposed stabilization treatment can be considered for future use by conservators.     

Effect of the size of the charged group on the properties of alkoxylated NFCs

The impact of the size of the charged group on the properties of alkoxylated NFC was studied by two chloroalkyl acid reagents. It was found that the employment of the larger 2-chloropropionic acid reagent leads to improved properties, e.g. higher fraction of nano-sized materials, and significantly better redispersion as compared to when the smaller monochloroacetic acid was employed. The differences in the impacts of the different reagents were hypothesized to be due to a more efficient disruption of the cohesion between the nanofibrils when a larger charged group was employed.     

Determination of Anthelmintic Pharmaceuticals in Wastewater by Solid-Phase Extraction and Thin-Layer Chromatography

JPC – Journal of Planar Chromatography – Modern TLC - The presented study describes the development, optimization, and validation of a method for the determination of four structurally...     

Airborne particles in the Miyagi Museum of Art in Sendai, Japan, studied by electron probe X-ray microanalysis and energy dispersive X-ray fluorescence analysis.

The presented work provides baseline data on the existing airborne conditions in the Miyagi Museum of Art in Sendai, Japan, during the summer of 2000. The chemical composition, size and indoor and outdoor origin of the suspended particulate matter were identified using a number of advanced X-ray techniques, such as Electron Probe X-Ray Microanalysis (EPXMA) and Energy Dispersive X-Ray Fluorescence Analysis (EDXRF). Our results, to the best of our knowledge, represent the first detailed study of the chemical nature of the indoor particulate matter in a Japanese museum and, as such, may contribute to future improvements of the air quality inside museums and to the lasting conservation of works of art.     

Agglutination of like-charged red blood cells induced by binding of beta2-glycoprotein I to outer cell surface

Plasma protein-mediated attractive interaction between membranes of red blood cells (RBCs) and phospholipid vesicles was studied. It is shown that beta(2)-glycoprotein I (beta(2)-GPI) may induce RBC discocyte-echinocyte-spherocyte shape transformation and subsequent agglutination of RBCs. Based on the observed beta(2)-GPI-induced RBC cell shape transformation it is proposed that the hydrophobic portion of beta(2)-GPI molecule protrudes into the outer lipid layer of the RBC membrane and increases the area of this layer. It is also suggested that the observed agglutination of RBCs is at least partially driven by an attractive force which is of electrostatic origin and depends on the specific molecular shape and internal charge distribution of membrane-bound beta(2)-GPI molecules. The suggested beta(2)-GPI-induced attractive electrostatic interaction between like-charged RBC membrane surfaces is qualitatively explained by using a simple mathematical model within the functional density theory of the electric double layer, where the electrostatic attraction between the positively charged part of the first domains of bound beta(2)-GPI molecules and negatively charged glycocalyx of the adjacent RBC membrane is taken into account.     

Determination of dithiothreitol in complex protein mixtures by HPLC-MS

Dithiothreitol (DTT) and other reducing agents are typically used in refolding processes of recombinant human proteins during their purification from inclusion bodies. Due to its toxicity, it is essential to monitor the clearance of DTT throughout the analytical flow from the refolding phase to the final formulated product. Here we report a direct, simple, and fast liquid chromatography method using UV and tandem mass spectrometry (MS/MS) detection for DTT evaluation in complex protein mixtures. In aqueous solution DTT exists as an equilibrium mixture of the oxidized and the reduced form (H(2)DTT --> DTT(ox)) and the quantitation tools should therefore be applicable to both forms in a single step or in multiple steps. Oxidation of DTT with aqueous copper(II) nitrate trihydrate solution was introduced to determine a single oxidized compound, i. e. DTT(ox). Proteins and other components of high molecular masses were separated from DTT(ox) by ultrafiltration. Consequently, efficient separation of the DTT(ox )from other flow-through mixture components (sugars, polymers, salts, protein stabilizers) was achieved on an Atlantis dC(18) column. After chromatographic separation, DTT(ox) was selectively identified by UV absorbance at 285 nm or by selected reaction monitoring, measuring signal transition between m/z 151 --> 105. The method was validated in terms of specificity, accuracy, precision, linearity, and limit of quantification and detection. A reversed-phase HPLC separation method with atmospheric pressure chemical ionization and MS/MS detection in negative ion mode is highlighted as a viable alternative to currently existing quantitation methods involving DTT derivatization and HPLC fluorescence detection. The described approach offers simple, straightforward, selective, and high-throughput DTT quantitation in protein mixtures.     

Parenchyma cell wall structure in twining stem of <Emphasis Type="Italic">Dioscorea balcanica</Emphasis>

Anatomical adaptation of liana plants includes structural changes in cell walls of different tissues: fibers, vessel elements and tracheids. However, the contribution of parenchyma cells to stem twining in liana plants is mostly unknown. The aim of this investigation is to determine changes in stem parenchyma cell walls that are correlated with the twinning process in liana plants. Parenchyma cell wall structure was studied on the stem cross sections of straight and twisted internodes of monocotyledonous liana Dioscorea balcanica, by different microscopy techniques: light microscopy, scanning electron microscopy, fluorescence detected linear dichroism microscopy and Fourier transform infrared microspectrometry. In addition, chemical analysis of the entire stem internodes was performed using photometric and chromatographic methods. Parenchyma cell walls of twisted D. balcanica internodes are characterized by: lower amounts of cellulose (obtained by FTIR microspectrometry) with different cellulose microfibril orientation (shown by Scanning electron microscopy), but no changes in “cellulose fibril order” (obtained by Differential polarization laser scanning microscopy); lower amounts of xyloglucan, higher amounts of xylan, higher amounts of lignin with modified organization—less condensed lignin (obtained by FTIR microspectrometry). At the same time, chemical analysis of the entire internodes did not show significant differences in lignin content and cell wall bound phenols related to stem twining, except for the presence of diferulate cross-links exclusively in twisted internodes. Our results indicate that adaptations to mechanical strain in D. balcanica stems involve modifications in parenchyma cell wall structure and chemistry, which provide decreased stiffness, higher strength and increased elasticity of twisted internodes.     

Performance of a nuclear microprobe to study giant marine aerosol particles

The scanning nuclear microprobe analytical facility of the IRMM was used to determine with PIXE major, minor and trace elements in individual giant marine aerosol particles, collected above the North Sea (particle size > 5 m Ø). The instrumentation is briefly described, and the experimental parameters chosen for these analyses are discussed. Elements with atomic numbers Z > 15 could be determined. Detection limits observed under the prevailing experimental conditions reached down to 50 fg in the case of Ti, V or Cr, corresponding to a mass content of 10 g/g in particles of 15 m size. Quantitative evaluation of the acquired spectra revealed basically three aerosol types in these samples: sea salt particles, sea salt combined with high contents of S, K and Ca, and particles rich in heavier elements (Ti, Cr, Fe, Ni). The agglomeration of several large particles forming a giant one could be visualised directly through the heterogeneity found in the elemental maps of such a particle.     

Synthesis and Structures of the Novel Pyridoxal Oxime Derivatives

Novel pyridoxal oxime derivatives were prepared and characterized by means of IR, ¹H and ¹³C NMR spectroscopy. The crystal structures of the 3-hydroxy-4-hydroxyiminomethyl-5-hydroxymethyl-1,2-dimethylpyridinium iodide 1 and 3-hydroxy-4-hydroxyiminomethyl-5-hydroxymethyl-1,2-dimethylpyridinium chloride monohydrate 2 were determined by X-ray analysis. The both compounds crystallize in the triclinic crystal system, space group P . Crystal data: 1 a = 6.286(2) Å, b = 8.748(4) Å, c = 11.736(4) Å, = 104.02(3)°, = 94.70(3)°, = 107.44(6)°, V = 589.0(4) ų, Z = 2, R = 0.0526; 2 a = 6.8980(5) Å, b = 8.6409(6) Å, c = 11.1777(6) Å, = 111.138(5)°, = 93.114(6)°, = 105.158(5)°, V = 591.57(7) ų, Z = 2, R = 0.0492. The bond distances and angles in both structures agree very well. The main difference between these structures was observed in the orientation of the hydroxymethyl group with respect to the pyridinium ring. In the both structures intramolecular hydrogen bond forming six-membered ring were observed. The intermolecular OsI hydrogen bonds in the crystal structure of the compound 1 form dimers. In the crystal structure of compound 2, the water molecules and chlorines build eight-membered rings, which are also connected to pyridinium cations by OsCl and OsO intermolecular hydrogen bonds forming a three-dimensional network.